Solidification characteristics and segregation behavior of a P-containing Ni-Fe-Cr-based alloy, considered as boiler and turbine materials in 700 degrees C advanced ultra-supercritical coal-fired power plants, have been investigated by differential thermal analysis and directional solidification quenching technique. Results reveal that P decreases the solidus temperature, but only has negligible influence on liquidus temperature. After P was added, the solidification sequence has no apparent change, but the width of the mushy zone increases and dendritic structures become coarser. Moreover, P increases the amount and changes the morphology of MC carbide. Energy-dispersive spectroscopy analysis reveals that P has obvious influence on the segregation behavior of the constitute elements with equilibrium partition coefficients (k(i)) far away from unity, whereas has negligible effect on the constituent elements with k(i) close to unity and has more influence on the final stage of solidification than at early stage. The distribution profiles reveal that P atoms pile up ahead of the solid/liquid (S/L) interface and strongly segregate to the interdendritic liquid region. The influence of P on solidification characteristics and segregation behavior of Ni-Fe-Cr-based alloy could be attributed to the accumulation of P ahead of the S/L interface during solidification.